Hierarchical Supramolecular Spinning of Nanofibers in a Microfluidic Channel: Tuning Nanostructures at a Dynamic Interface

One of the fundamental problems in supramolecular chemistry, as well as in material sciences, is how to control the self‐assembly of polymers on the nanometer scale and how to spontaneously organize them towards the macroscopic scale. To overcome this problem, inspired by the self‐assembly systems in nature, which feature the dynamically controlled self‐assembly of biopolymers, we have previously proposed a self‐assembly system that uses a dynamic liquid/liquid interface with dimensions in the micrometer regime, thereby allowing polymers to self‐assemble under precisely controlled nonequilibrium conditions. Herein, we further extend this system to the creation of hierarchical self‐assembled architectures of polysaccharides. A natural polysaccharide, β‐1,3‐glucan (SPG), and water were injected into opposite “legs” of microfluidic devices that had a Y‐shape junction, so that two solvents would gradually mix in the down stem, thereby causing SPG to spontaneously self‐assemble along the flow in a head‐to‐tail fashion, mainly through hydrophobic interactions. In the initial stage, several SPG nanofibers would self‐assemble at the Y‐junction owing to the shearing force, thereby creating oligomers with a three‐way junction point. This unique structure, which could not be created through conventional mixing procedures, has a divergent self‐assembly capability. The dynamic flow allows the oligomers to interact continuously with SPG nanofibers that are fed into the Y‐junction, thus amplifying the nanostructure along the flow to form SPG networks. Consequently, we were able to create stable, centimeter‐length macroscopic polysaccharide strands under the selected flow conditions, which implies that SPG nanofibers were assembled hierarchically in a supramolecular fashion in the dynamic flow. Microscopic observations, including SEM and AFM analysis, revealed the existence of clear hierarchical structures inside the obtained strand. The network structures self‐assembled to form sub‐micrometer‐sized fibers. The long fibers further entangled with each other to give stable micrometer‐sized fibers, which finally assembled to form the macroscopic strands, in which the final stabilities in the macroscopic regime were governed by that of the network structures in the nanometer regime. Thus, we have exploited this new supramolecular system to create hierarchical polymeric architectures under precisely controlled flow conditions, by combining the conventional supramolecular strategy with microfluidic science.     

Metal-insulator transition in amorphous Si1−xCrx films

The electrical conductivity of the amorphous Si_1−xCr_x films prepared by vacuum evaporation and sputtering was measured down to 40mK. In both films we observed a continuous metal-insulator transition. The electrical conductivity at low temperatures and the critical behavior are explained in terms of the scaling theory for interacting electrons. Whereas, present results support neither the scaling law proposed by Möbius et al. nor the existance of σ_min reported in the same system.     

Revised structure of diastereomeric 3,8-di-t-butylspiro[4,4]nonane-1,6-diones

The recently assigned diastereomeric configuration of 3,8-di-t-butylspiro[4.4]nonane-1,6-dione has been revised based on the X-ray analysis.     

Oligosilane-nanofibers can be prepared through fabrication of permethyldecasilane within a helical superstructure of schizophyllan

[chemical structure: see text]. Schizophyllan can interact with permethyldecasilane to produce the corresponding decasilane-nanofiber, in which the decasilane adopts helical conformations in a tubular hollow created by the helical superstructure of schizophyllan.     

Polyaddition reactions of bisethyleneureas and 1,1,3,3-diethyleneurea with polymethylene dimercaptans in LiCl-dimethylformamide

Polyaddition reactions of 1,1′-tetramethylenebis(3,3-ethyleneurea) (IIa), 1,1′-octamethylenebis(3,3-ethyleneurea) (IIb), 1,1′-p-phenylenebis(3,3-ethyleneurea) (IIc), 1,1′-(4,4′-diphenylmethane)bis(3,3-ethyleneurea) (IId) and 1,1,3,3-diethyleneurea (III) with polymethylene dimercaptans were investigated. 1,1′-Polymethylenebis(3,3-ethyleneureas) and polymethylene dimercaptans successfully reacted at 80–95°C. in the presence of triethylamine to give poly(urea sulfides) with intrinsic viscosities up to 1.1 in about 90% yield when dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone containing lithium chloride as a solvent were used. The other ethyleneureas, however, failed to give high molecular weight polymers.     

Near-IR emission of Nd(III) encaged in nanosized zeolites

The near-IR emission of Nd(III) with the highest quantum yield (9.5%) in organic media was successfully observed for the first time by using bis-(perfluoromethylsulfonyl)amide (PMS) as a low vibrational ligand of the ion and TMA⁺-containing FAU zeolite nanocrystallites (TMA-nanoFAU) as a host matrix. Treatments such as deuteration and thermal treatments at high temperatures were ineffective for the strong emission of Nd(III) within TMA-nano-FAU. Judd-Ofelt analysis revealed that the ligation of PMS with the Nd(III) ion occurred easily, because the ions remained in the super cages without migrating into inner cages due to the hindrance of TMA⁺ ions occupying in the sodalite cages. The emission intensity of TMA-nano-FAU treated with PMS increased with the Nd(III)-loading level. The emission decays did not follow simple first-order kinetics and the average lifetime became longer with increasing Nd(III)-loading level. The short lifetimes at low loading levels and the long lifetimes at high loading level were attributed to Nd(PMS)₃ complexes formed with coordinating water molecules and [Nd(PMS)]-zeolite complexes without coordinating water molecules, respectively.     

Creation of polynucleotide-assisted molecular assemblies in organic solvents: general strategy toward the creation of artificial DNA-like nanoarchitectures

The influence of added polynucleotide on the gelation ability of nucleobase-appended organogelators was investigated. Uracil-appended cholesterol gelator formed a stable organogel in polar organic solvents such as n-butanol. It was found that the addition of the complementary polyadenylic acid (poly(A)) not only stabilizes the gel but also creates the helical structure in the original gel phase. Thymidine and thymine-appended gelators can form stable gel in apolar solvents, such as benzene, where poly(A)-lipid complex can act as a complementary template for the gelator molecules to create the fibrous composites. Based on these findings, we can conclude that self-assembling modes and gelation properties of nucleobase-appended organogelators are controllable by the addition of their complementary polynucleotide in organic solvents. We believe, therefore, that the present system can open the new paths to accelerate development of well-controlled one-dimensional molecular assembly systems, which would be indispensable for the creation of novel nanomaterials based on organic compounds.     

Stereoselective Synthesis and Physicochemical Properties of Liquid‐Crystal Compounds Possessing a trans‐2,5‐Disubstituted Tetrahydropyran Ring with Negative Dielectric Anisotropy

Three stereoselective syntheses and the physicochemical properties of trans,trans‐5‐(4‐ethoxy‐2,3‐difluorophenyl)‐2‐(4‐propylcyclohexyl)tetrahydropyran, which is an important liquid‐crystal compound with a large negative dielectric anisotropy (Δε=?7.3), are described. The key step in the construction of the trans‐2,5‐disubstituted tetrahydropyran ring in the first approach involved a benzylic cation mediated intramolecular olefin cyclization of a 2‐allyloxy‐1‐arylethanol derivative. The second method included the Et₂Zn‐induced 1,2‐aryl shift of a bromohydrin obtained from a hetero‐Diels–Alder reaction, followed by stereoselective bromination. The third approach utilized the hetero‐Diels–Alder reaction of trans‐4‐propylcyclohexanecarboxaldehyde and a 2‐aryl‐3‐(trimethylsilyl)oxy‐1,3‐butadiene, followed by stereoselective protonation. From results obtained by using a quantum chemical calculation method, the reason why the target compound shows a large negative Δε value is discussed.